EP1348693A1 - Verfahren zur Herstellung von Diazonaphthochinonsulfonylchloriden mit Diphosgen und Triphosgen - Google Patents

Verfahren zur Herstellung von Diazonaphthochinonsulfonylchloriden mit Diphosgen und Triphosgen Download PDF

Info

Publication number
EP1348693A1
EP1348693A1 EP02007068A EP02007068A EP1348693A1 EP 1348693 A1 EP1348693 A1 EP 1348693A1 EP 02007068 A EP02007068 A EP 02007068A EP 02007068 A EP02007068 A EP 02007068A EP 1348693 A1 EP1348693 A1 EP 1348693A1
Authority
EP
European Patent Office
Prior art keywords
sodium salt
naphthoquinone
diazo
diphosgene
triphosgene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP02007068A
Other languages
English (en)
French (fr)
Other versions
EP1348693B1 (de
Inventor
Vummadi Venkat Reddy
Maruthy Janaki Ram Reddy
Vaidya Jayathirtha Rao
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Council of Scientific and Industrial Research CSIR
Original Assignee
Council of Scientific and Industrial Research CSIR
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Council of Scientific and Industrial Research CSIR filed Critical Council of Scientific and Industrial Research CSIR
Priority to EP02007068A priority Critical patent/EP1348693B1/de
Priority to DE60222376T priority patent/DE60222376T2/de
Publication of EP1348693A1 publication Critical patent/EP1348693A1/de
Application granted granted Critical
Publication of EP1348693B1 publication Critical patent/EP1348693B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/22Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00Systems containing two condensed rings
    • C07C2602/02Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04One of the condensed rings being a six-membered aromatic ring
    • C07C2602/10One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline

Definitions

  • the present invention relates to a process for the preparation of diazonaphthoquinonesulfonylchlorides, useful intermediates in electronic industry and dye industry.
  • This research pertains to a method of preparation of diazonaphthoquinonesulfonylchlorides having formula 1-3 from corresponding diazonaphthoquinonesulfonic acid or its sodium salt, using diphosgene or triphosgene.
  • Another method involves use of thionylchloride with dimethylformamide as catalyst with the corresponding diazonaphthoquinonesulfonic acid or its salt. This method also suffers the disadvantages like heating the reaction mixture, use of excess thionylchloride and evolution of sulfurdioxide and hydrogenchloride gases (CA, vol. 96, 34766b, Khim. Process, year 1981, p505 (Russ)).
  • Another method involves use of chlorosulfonic acid in combination with thionylchloride along with the corresponding diazonaphthoquinonesulfonic acid or its salt.
  • the main disadvantages are the same as mentioned above (CA, vol. 105, 208620w, Ger (East) 272,511, year 1985 and DD 234, 000, year 1986; CA vol. 112, 178384x, Ger (East) DD 269,846, year 1989, Ger (East) 312,180, year 1988; CA, vol. 124, 302642u, JP 08,27,098, year 1996; CA, vol. 125, 170873d, RO 104,624, year 1994).
  • Yet another method involves is the use of phosgene (toxic gas) with the corresponding diazonaphthoquinonesulfonic acid or its salt.
  • This method has the optimum temperature conditions but the greatest disadvantage is the use of toxic phosgene gas (CA, vol. 102, 113031d, JP 59,196,860, year 1984; CA, vol. 105, 60439w, EP 178,356, year 1986).
  • the present invention describes an altogether new process for the preparation of diazonaphthoquinonesulfonylchlorides by reacting the corresponding diazonaphthoquinone sulfonic acid or its salt either with diphosgene or triphosgene in presence of triethylamine base in dichloromethane solvent.
  • Various solvents like, chloroform, 1,2-dichloroethane, benzene, toluene, acetonitrile, benzonitrile, nitrobenzene and others are also used.
  • Organic bases like tributylamine, pyridine, tripropylamine, N,N-dimethylaniline, N,N-diethylamine and other bases are also employed.
  • Dichloromethane as solvent and triethylamine as organic base were preferred.
  • the temperature of the reaction was varied over -50 to +5°C and -40°C is the preferred temperature condition.
  • the base is found to be essential for the reaction to be conducted and without the organic base there is no reaction occurs.
  • the 2 mole equivalent ratio of base is the right combination found.
  • the work up procedure and isolation of the product diazonaphthoquinonesulfonylchloride is very simple and rapid. After the reaction the organic base and the solvent can be recovered. After the isolation of the product, the remaining filtrate contains the unreacted diazonaphthoquinonesulfonic acid as judged by the UV-Visible absorption data.
  • the products were characterized by the spectral data.
  • the present invention provides a process for the preparation of diazonaphthoquinonesulfonylchlorides of formula 1-3, using diphosgene or triphosgene which comprises reacting diazonaphthoquinonesulfonicacid sodium salt with an organic base in a molar ratio ranging between 1: 1.5 - 1: 2.5 in an organic solvent in the presence of diphosgene or triphosgene in a molar ratio of diazonaphthoquinonesulfonicacid sodium salt to diphosgene or triphosgene in the range of 1:1-1:1.5 ,at a temperature ranging from -50 °C to 5°C, for a period ranging from 40-90 min, subsequently increasing the temperature to 20-25°C, removing the solvent and base from the above said reaction mixture under vacuum to obtain the yellow powder product and re-precipitating the desired product in ice water.
  • the organic base used is selected from the group consisting of triehylamine, tributylamine, pyridine, tripropylamine, N,N-dimethylaniline and N,N-diethylamine.
  • organic base used is triehylamine.
  • the organic solvent used is selected from the group consisting of chloroform, 1,2-dichloroethane, benzene, toluene, acetonitrile, benzonitrile, nitrobenzene and dichloromethane.
  • organic solvent used is dichloromethane.
  • the molar ratio of diazonaphthoquinonesulfonicacid sodium salt to organic base used is 1:2.
  • the molar ratio of diazonaphthoquinone sulfonicacid sodium salt to triphosgene or diphosgene used is 1:1.
  • the diazonaphthoquinonesulfonicacid sodium salt used is selected from 2-Diazo-1-naphthoquinone-4-sulfonic acid sodium salt, 2-Diazo-1-naphthoquinone-5-sulfonic acid sodium salt and 1-Diazo-2-naphthoquinone-4-sulfonic acid sodium salt.
  • the diazonaphthoquinonesulfonul chloride obtained is selected from 2-Diazo-1-naphthoquinone-4-chloride of formula 1, 2-Diazo-1-naphthoquinone-5-sulfonulchloride of formula 2, and 1-Diazo-2-naphthoquinone-4-sulfonulchloridesulfonulchloride of formula 3.
  • 2-Diazo-1-naphthoquinone-4-sulfonic acid sodium salt (2.72g; 0.01mol) was taken into 25 ml of dichloromethane and cooled to -50°C.
  • triethylamine (2.02g; 0.02mol) to the above solution and maintained the temperature at -50°C.
  • diphosgene (2.18g; 0.011mol) in 15 ml dichloromethane very slowly and maintaining the temperature at -50°C with stirring over a period of 20min.
  • the reaction mixture was stirred magnetically for 60 min at -50°C. Reaction mixture was brought to room temperature and then dichloromethane and triethylamine was removed under vacuum.
  • the remaining yellow powder was poured into ice water after 5 min of holding it in ice water the precipitate formed was filtered, washed with ice water and dried in a vacuum desiccator.
  • the dried 2-diazo-1-naphthoquinone-4-sulfonylchloride weight was 2.14g(0.0080mol) yield 80% m.p 138 -140°C.
  • the 2-diazo-1-naphthoquinone-4-sulfonylchloride was characterized by UV-Visible absorption, 1 H-nmr and Mass spectrometry.
  • 2-Diazo-1-naphthoquinone-4-sulfonic acid sodium salt (10g; 0.037mol) was taken into 90 ml of dichloromethane and cooled to -50°C.
  • triethylamine (7.4g; 0.073mol) to the above solution and maintained the temperature at -50°C.
  • the reaction mixture was stirred magnetically for 60 min at -50°C. Reaction mixture was brought to room temperature and then dichloromethane and triethylamine was removed under vacuum.
  • the remaining yellow powder was poured into ice water, after 5 min of holding it in ice water the precipitate formed was filtered, washed with ice water and dried in a vacuum desiccator.
  • the dried 2-diazo-1-naphthoquinone-4-sulfonylchloride weight was 7.93g (0.0296mol) yield 80%.
  • 2-Diazo-1-naphthoquinone-5-sulfonic acid sodium salt (2.72g; 0.01mol) was taken into 25 ml of dichloromethane and cooled to -50°C.
  • triethylamine (2.02g; 0.02mol) to the above solution and maintained the temperature at -50°C.
  • diphosgene (2.18g; 0.011mol) in 15 ml dichloromethane very slowly and maintaining the temperature at -50°C with stirring over a period of 20min.
  • the reaction mixture was stirred magnetically for 60 min at -50°C. Reaction mixture was brought to room temperature and then dichloromethane and triethylamine was removed under vacuum.
  • the remaining yellow powder was poured into ice water, after 5 min of holding it in ice water the precipitate formed was filtered, washed with ice water and dried in a vacuum desiccator.
  • the dried 2-diazo-1-naphthoquinone-5-sulfonylchloride weight was 2.14g(0.0080mol) yield 80% mp 135-138°C.
  • the 2-diazo-1-naphthoquinone-5-sulfonylchloride was characterized by UV-Visible absorption, 1 H-nmr and Mass spectrometry.
  • 2-Diazo-1-naphthoquinone-5-sulfonic acid sodium salt (10g; 0.037mol) was taken into 90ml of dichloromethane and cooled to -50°C.
  • triethylamine (7.4g; 0.073mol) to the above solution and maintained the temperature at -50°C.
  • diphosgene (7.35g; 0.037mol) in 15ml dichloromethane very slowly and maintaining the temperature at -50°C with stirring over a period of 30min.
  • the reaction mixture was stirred magnetically for 60 min at -50°C. Reaction mixture was brought to room temperature and then dichloromethane and triethylamine was removed under vacuum.
  • the remaining yellow powder was poured into ice water after 5 min of holding it in ice water the precipitate formed was filtered, washed with ice water and dried in a vacuum desiccator.
  • the dried 2-diazo-1-naphthoquinone-5-sulfonylchloride weight was 7.93g(0.0296mol) yield 80%.
  • Example 5 1-Diazo-2-naphthoquinone-4-sulfonic acid sodium salt (2.72g; 0.01mol) was taken into 25 ml of dichloromethane and cooled to -50°C. Added triethylamine (2.02g; 0.02mol) to the above solution and maintained the temperature at -50°C. Then added diphosgene (2.18g; 0.011mol) in 15 ml dichloromethane very slowly and maintaining the temperature at -50°C with stirring over a period of 20 min. The reaction mixture was stirred magnetically for 60 min at -50°C. Reaction mixture was brought to room temperature and then dichloromethane and triethylamine was removed under vacuum.
  • the remaining yellow powder was poured into ice water, after 5 min of holding it in ice water the precipitate formed was filtered, washed with ice water and dried in a vacuum desiccator.
  • the dried 1-diazo-2-naphthoquinone-4-sulfonylchloride weight was 2.14 g(0.0080mol) yield 80%, m.p 138 -140°C.
  • the 1-diazo-2-naphthoquinone-4-sulfonylchloride was characterized by UV-Visible absorption, 1 H-nmr and Mass spectrometry.
  • 2-Diazo-1-naphthoquinone-4-sulfonic acid sodium salt (2.72g; 0.01mol) was taken into 25 ml of dichloromethane and cooled to -50°C.
  • triethylamine (2.02g; 0.02 mol) to the above solution and maintained the temperature at -50°C.
  • triphosgene (3.2g; 0.011 mol) in 15 ml dichloromethane very slowly and maintaining the temperature at -50°C with stirring over a period of 20 min.
  • the reaction mixture was stirred magnetically for 60 min at -50°C. Reaction mixture was brought to room temperature and then dichloromethane and triethylamine were removed under vacuum.
  • the remaining yellow powder was poured into ice water, after 5min of holding it in ice water the precipitate formed was filtered, washed with ice water and dried in a vacuum desiccator.
  • the dried 2-diazo-1-naphthoquinone-4-sulfonylchloride weight was 2.14 g (0.0080mol) yield 80%.
  • 2-Diazo-1-naphthoquinone-5-sulfonic acid sodium salt (2.72g; 0.01 mol) was taken into 25 ml of dichloromethane and cooled to -50°C.
  • triethylamine (2.02g; 0.02 mol) to the above solution and maintained the temperature at -50°C.
  • triphosgene (3.2g; 0.011 mol) in 15 ml dichloromethane very slowly and maintaining the temperature at -50°C with stirring over a period of 20 min.
  • the reaction mixture was stirred magnetically for 60 min at -50°C. Reaction mixture was brought to room temperature and then dichloromethane and triethylamine were removed under vacuum.
  • the remaining yellow powder was poured into ice water, after 5 min of holding it in ice water the precipitate formed was filtered, washed with ice water and dried in a vacuum desiccator.
  • the dried 2-diazo-1-naphthoquinone-5-sulfonylchloride weight was 2.14 g (0.0080mol) yield 80%.
  • 1-Diazo-2-naphthoquinone-4-sulfonic acid sodium salt (2.72g; 0.01 mol) was taken into 25 ml of dichloromethane and cooled to -50°C.
  • triethylamine (2.02g; 0.02 mol) to the above solution and maintained the temperature -50°C.
  • triphosgene (3.2g; 0.011 mol) in 15 ml dichloromethane very slowly and maintaining the temperature -50°C with stirring over a period of 20 min.
  • the reaction mixture was stirred magnetically for 60 min at -50°C. Reaction mixture was brought to room temperature and then dichloromethane and triethylamine was removed under vacuum.
  • the remaining yellow powder was poured into ice water, after 5 min of holding it in ice water the precipitate formed was filtered, washed with ice water and dried in a vacuum desiccator.
  • the dried 1-diazo-2-naphthoquinone-4-sulfonylchloride weight was 2.14 g (0.0080mol) yield 80%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP02007068A 2002-03-27 2002-03-27 Verfahren zur Herstellung von Diazonaphthochinonsulfonylchloriden mit Diphosgen und Triphosgen Expired - Lifetime EP1348693B1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP02007068A EP1348693B1 (de) 2002-03-27 2002-03-27 Verfahren zur Herstellung von Diazonaphthochinonsulfonylchloriden mit Diphosgen und Triphosgen
DE60222376T DE60222376T2 (de) 2002-03-27 2002-03-27 Verfahren zur Herstellung von Diazonaphthochinonsulfonylchloriden mit Diphosgen und Triphosgen

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP02007068A EP1348693B1 (de) 2002-03-27 2002-03-27 Verfahren zur Herstellung von Diazonaphthochinonsulfonylchloriden mit Diphosgen und Triphosgen

Publications (2)

Publication Number Publication Date
EP1348693A1 true EP1348693A1 (de) 2003-10-01
EP1348693B1 EP1348693B1 (de) 2007-09-12

Family

ID=27798817

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02007068A Expired - Lifetime EP1348693B1 (de) 2002-03-27 2002-03-27 Verfahren zur Herstellung von Diazonaphthochinonsulfonylchloriden mit Diphosgen und Triphosgen

Country Status (2)

Country Link
EP (1) EP1348693B1 (de)
DE (1) DE60222376T2 (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007026374A1 (en) * 2005-09-01 2007-03-08 Council Of Scientific And Industrial Research A single pot process for the preparation of diazonaphthoquinonesulfonyl ester
EP2581363A1 (de) * 2011-10-14 2013-04-17 Lonza Ltd Flüssiges Phosgenierungsreagenz
CN105693564A (zh) * 2016-04-02 2016-06-22 田菱精细化工(大连)有限公司 一种萘醌磺酰氯的合成方法
CN105753743A (zh) * 2016-04-02 2016-07-13 田菱精细化工(大连)有限公司 一种合成萘醌磺酰氯的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102408364B (zh) * 2010-09-26 2014-11-12 中化蓝天集团有限公司 一种制备对甲苯磺酰氯的方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
E. SAUER, ET AL.: "Sulfochlorierung von 1,2-Naphthochinondiazid-(2) mit Chlorsulfonsäure", JOURNAL FÜR PRAKTISCHE CHEMIE, vol. 333, no. 3, 1991, Leipzig, DE, pages 467 - 473, XP000925654, ISSN: 0021-8383 *
R.C. REYNOLDS, ET AL.: "Synthesis of thymidine dimers containig internucleoside sulphonate and sulphonamide linkages", JOURNAL OF ORGANIC CHEMISTRY, vol. 57, no. 11, 22 May 1992 (1992-05-22), American Chemical Society, Washington, DC, US, pages 2983 - 2985, XP002211505, ISSN: 0022-3263 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007026374A1 (en) * 2005-09-01 2007-03-08 Council Of Scientific And Industrial Research A single pot process for the preparation of diazonaphthoquinonesulfonyl ester
JP2009507013A (ja) * 2005-09-01 2009-02-19 カウンシル・オブ・サイエンティフィック・アンド・インダストリアル・リサーチ ジアゾナフトキノンスルホニルエステルの製造のためのシングルポットプロセス
EP2581363A1 (de) * 2011-10-14 2013-04-17 Lonza Ltd Flüssiges Phosgenierungsreagenz
CN105693564A (zh) * 2016-04-02 2016-06-22 田菱精细化工(大连)有限公司 一种萘醌磺酰氯的合成方法
CN105753743A (zh) * 2016-04-02 2016-07-13 田菱精细化工(大连)有限公司 一种合成萘醌磺酰氯的方法

Also Published As

Publication number Publication date
DE60222376T2 (de) 2008-05-29
DE60222376D1 (de) 2007-10-25
EP1348693B1 (de) 2007-09-12

Similar Documents

Publication Publication Date Title
HARVILL et al. The Synthesis of 1, 5-disubstituted tetrazoles
DK170335B1 (da) Fremgangsmåde til fremstilling af 5-cyano-10-nitro-5H-dibenz(b,f)azepin
EP1348693B1 (de) Verfahren zur Herstellung von Diazonaphthochinonsulfonylchloriden mit Diphosgen und Triphosgen
US6559291B1 (en) Process for the preparation of diazonaphthoquinonesulfonylchlorides using diphosgene and triphosgene
EP1945605B1 (de) Verfahren zur herstellung substituierter anisidine
JP3162232B2 (ja) 二環式芳香族スルホン酸、塩化スルホニルおよびスルホンアミドの合成
EP0135304B1 (de) Verfahren zur Herstellung von substituierten Benzamiden
JP4159022B2 (ja) ジホスゲン及びトリホスゲンを使用したジアゾナフトキノンスルホニルクロリドの調製法
US10752585B2 (en) Process for the preparation of Zafirlukast and analogs thereof
WO2020072616A1 (en) Process and intermediates for the preparation of certain nematicidal sulfonamides
US4355178A (en) Process for the preparation of substituted acyl ureas
JP5033933B2 (ja) N−置換−2−アミノ−4−(ヒドロキシメチルホスフィニル)−2−ブテン酸の製造法
US4578513A (en) Process for preparing phenylisopropylurea compounds
JP2719841B2 (ja) チオ尿素誘導体及びその製造方法
JP2020537680A (ja) 除草性ピリダジノン化合物を製造するプロセス
Conway et al. An Efficient One-Pot Synthesis of Hippuric Acid Ethyl Ester Derivatives
KR100277262B1 (ko) 2-아미노-5-메틸-피리딘의 제조방법
RU2575174C1 (ru) СПОСОБ ПОЛУЧЕНИЯ ПРОИЗВОДНЫХ 5,6-ДИГИДРОПИРРОЛО[2,1-a]ИЗОХИНОЛИНОВ, СОДЕРЖАЩИХ В ПОЛОЖЕНИИ 2 ФУНКЦИОНАЛЬНУЮ ГРУППУ
CA2295912A1 (en) Process for the preparation of 2-alkylthio benzoic acid derivatives
EP3166404B1 (de) Verbessertes verfahren zur herstellung von 4- (1- (4- (perfluoroethoxy)phenyl)-1h-1,2,4-triazol-3-yl)benzoylazid
PL138793B1 (en) Method of obtqining nysatidine
KR20010073096A (ko) 옥사졸 화합물의 제조방법
JP2671401B2 (ja) α‐アミノチオアセトアミド誘導体およびその製造法
JP2003160569A (ja) 塩基触媒によるキナゾリン誘導体の製造法
JPS6126540B2 (de)

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

17P Request for examination filed

Effective date: 20031211

AKX Designation fees paid

Designated state(s): CH DE FR GB LI

17Q First examination report despatched

Effective date: 20050513

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): CH DE FR GB LI

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 60222376

Country of ref document: DE

Date of ref document: 20071025

Kind code of ref document: P

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: E. BLUM & CO. AG PATENT- UND MARKENANWAELTE VSP

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20080613

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20080327

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080327

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20150319

Year of fee payment: 14

Ref country code: DE

Payment date: 20150318

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20150327

Year of fee payment: 14

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60222376

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20161130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160331

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160331

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160331

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20161001